Bloom-resistant benzotriazole UV absorbers and compositions stabilized therewith

ABSTRACT

Benzotriazole UV absorbers substituted with an ultra long ester or amide moiety wherein the ester or amide group is a hydrocarbyl group of 25 to 100 carbon atoms or is a group of alkyl of 25 to 100 carbon atoms interrupted by 5 to 39 oxygen atoms and terminated with an omega—OH or an omega—OR group exhibit excellent stabilization efficacy while they concomitantly do not bloom when incorporated into polyolefin films. These benzotriazole UV absorbers also provide excellent protection to white, dyed, dipped, unscented and/or scented candle wax from discoloration and degradation.

This application is a continuation-in-part of application Ser. No.09/496,084, filed on Feb. 1, 2000 now U.S. Pat. No. 6,380,285.

This invention pertains to new benzotriazole UV absorbers having anultra long ester or amide moiety attached to the molecule are veryefficacious as UV absorbers while not blooming when incorporated intopolyolefin films and for candle wax.

BACKGROUND OF THE INVENTION

In the area of all stabilizers such as antioxidants, UV absorbers, lightstabilizers and the like, the original stabilizers are often simple,relatively inexpensive molecules involving some warhead moiety. Asparticular end-use application and new polymer substrates becomeimportant, molecular adjustments to these original stabilizers are madeto meet the new requirements.

An example of this is seen in U.S. Pat. No. 4,713,475 where someoriginal hindered phenolic antioxidant molecules are modified to containlong chain ester moieties for combatibility and solubilityconsiderations in new substrates.

There have been some attempts to put long chain alkyl ester moieties onbenzotriazole UV absorbers as seen in U.S. Pat. No. 5,705,474 whichdescribe fabric softeners where one component is a benzotriazole UVabsorber substituted by an alkyl ester of 1 to 22 carbon atoms. No longchain ester is specifically described or exemplified in this reference.

European Patent Application 315,155 A2 describes some negative typesilver halide photographic material which contain developmentaccelerators which are inter alia benzotriazoles substituted on thebenzo ring by dialkylaminoalkyl amide groups. None of these materialsare UV absorbers and are clearly structurally different from the instantcompounds. Likewise, U.S. Pat. No. 4,778,728 describes somebenzotriazole corrosion inhibitors which are structurally very differentfrom the instant compounds.

WO 97/42261 describes amide functional UV absorbers which resistblooming and migration which are inter alia benzotriazole UV absorberssubstituted on the phenyl ring by —CONH-alkyl amide moieties having upto 18 carbon atoms in the alkyl chain. The instant long chain alkylester or amide compounds do not overlap with these amide compounds.Indeed, the instant compounds have 25-100 carbon atoms for each alkylgroup.

U.S. Pat. Nos. 4,853,471, 4,973,702 and 5,032,498 describe benzotriazoleUV absorbers substituted on the phenyl ring by long chain alkyl estermoieties of up to 18 carbon atoms which can be interrupted by —O— and/orsubstituted by OH.

U.S. Pat. Nos. 5,280,124 and 5,977,219 and copending application Ser.No. 09/234,880 describe benzotriazole UV absorbers substituted on thephenyl ring by long chain alkyl ester groups of up to 24 carbon atomsand on the benzo ring with electron withdrawing groups in the5-position. When the instant compounds are unsubstituted on the benzoring, the phenyl ring can be substituted by long chain alkyl estergroups of 20 to 100 carbon atoms.

Additionally, the instant compounds are useful in protecting candlesfrom discoloration.

Candles have been known for many centuries going back to the eighthcentury B.C. The nature of candles is described in Ullmann'sEncyclopedia of Industrial Chemistry, Volume AS at pages 29-30 where itis seen that candles are made from paraffin, beeswax and stearin asbasic materials, and where a host of additives may also be present.

It is not surprising that with candles and wax becoming increasinglymore important attention was paid as to how to stabilize said materials.At the National Candle Association Meeting in Houston, 1994, R. van derVennet presented a paper on “Antioxidants in Wax—Replacement of BHT”touting the use of Vitamin E (tocopherol) as an antioxidant to preventthe yellowing of wax when oxidized. WO 94/13736 describes the sameinvention.

EP 359,488 A3 and EP 133,964 B1 describe stabilized waxes used incosmetics where the waxes are the same or similar to those used incandles.

EP 5,922 A1 describes lip cosmetics where the waxes are useful inlipsticks and are related to those useful in candles.

U.S. Pat. No. 5,879,694 describes in detail transparent gel candles bothin composition and structure. The use of BHT as an antioxidant ismentioned.

At the National Candle Association Technical Meeting on Apr. 16, 1998,F. A. Ballentine et al., presented a paper entitled “Inhibiting ColorFading of Dyed Candles with CYASORB® Light Absorbers” in which thegeneral theories of thermal oxidation and photodegradation are discussedalong with data on the effect of light absorbers on color stability ofdyed candle waxes. The light absorbers compared are4-octyloxy-2-hydroxybenzophenone UV-531; 4-methoxy-2-hydroxybenzophenoneUV-9; 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole UV-5365;2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole UV-5411 and2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole UV-2337).

U.S. Pat. No. 5,964,905 teaches dyed and scented candle gels containingtriblock copolymers and a hydrocarbon oil of high flash point. Thisreference teaches that a light (UV) absorber may be used to improve theshelf stability of the candle color when exposed to visible orultraviolet light. Two preferred absorbers are ethylhexylp-methoxycinnamate (PARSOL® MCX, Roche) and2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole (CYASORB® 5411,Cytec).

Japanese Hei 5-93164 discloses the use of benzotriazole UV absorbers andhindered amines in stabilizing pigmented wax crayons.

WO 00/22037 describes the stabilization of solid, shaped and colored waxarticles using a malonate UV absorber which may be substituted by ahindered amine group.

DETAILED DISCLOSURE

The instant invention pertains to new benzotriazole UV absorbers whichare not only effective UV absorbers, but also very resistant to bloomingwhen incorporated into polyolefin films, particularly polyethylenefilms.

More particularly, the instant benzotriazoles are of formula I, II orIII

wherein

G₁ and G₁′ are independently hydrogen or halogen,

G₂ and G₂′ are independently hydrogen, halogen, nitro, cyano, E₃SO—,E₃SO₂—, —COOG₃, perfluoroalkyl of 1 to 12 carbon atoms, —P(O)(C₆H₅)₂,—CO—G₃, —CO—NH—G₃, —CO—N(G₃)₂, —N(G₃)—CO—G₃,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight of branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 4 alkyl of 1 to 4 carbon atoms; or G₃ is T₁ or T₂,

E₁ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 4 alkyl of 1 to 4 carbon atoms; or E₁ is alkyl of 1 to 24carbon atoms substituted by one or two hydroxy groups; or E₁ is thegroup —(CH₂)_(m)—CO—X—T₁ where m is 0, 1 or 2; or E₁ is the group—(CH₂)_(p)—X—CO—T₂ where p is 1, 2 or 3,

E₂ and E₂′ are independently straight or branched alkyl chain of 1 to 24carbon atoms, straight or branched chain alkenyl of 2 to 18 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms, phenyl, or said phenyl or said phenylalkyl substituted on thephenyl ring by one to three alkyl of 1 to 4 carbon atoms; or E₂ and E₂′are independently said alkyl of 1 to 24 carbon atoms or said alkenyl of2 to 18 carbon atoms substituted by one or more —OH, —OCOE₁₁, —OE₄,—NH₂, —NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixtures thereof, where E₄ isstraight or branched chain alkyl of 1 to 24 carbon atoms; or said alkylor said alkenyl interrupted by one or more —O—, —NH— or —NE₄— groups ormixtures thereof and which can be unsubstituted or substituted by one ormore —OH, —OE₄ or —NH₂ groups or mixtures thereof; or E₄ is T₁ or T₂; orE₂ and E₂′ are independently (CH₂)_(m)—CO—X—T₁ or —(CH₂)_(p)—X—CO—T₂,

X is —O— or —N(E₁₆)—,

E₁₆ is hydrogen, C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygenatoms, or is cyclohexyl or C₇-C₁₅aralkyl,

E₁₁ is a straight or branched chain C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl,straight or branched chain C₂-C₁₈alkenyl, C₆-C₁₄aryl or C₇-C₁₅aralkyl;or E₁₁ is T₁ or T₂,

E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbonatoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atomsor said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms,

L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbonatoms, benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylylene orcycloalkylidene, and

T is —SO—, —SO₂—, —SO—E—SO—, —SO₂—E—SO₂—, —CO—, —CO—CH₂—CO—, —CO—E—CO—,—COO—E—OCO— or —CO—NG₅—E—NG₅—CO—,

where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12carbon atoms, or alkylene interrupted or terminated by cyclohexylene of8 to 12 carbon atoms;

G₅ is G₃ or hydrogen,

T₁ is straight or branched chain alkyl of 25 to 100 carbon atoms, orsaid alkyl substituted by one hydroxyl group and interrupted by one oxamoiety, or a mixture of such alkyl moieties; or

T₁ is —(R—O)_(n)—R—OG_(x) where R is ethylene, propylene, trimethylene,1,2-butylene or tetramethylene, and n is 6 to 49 so that the totalnumber of carbon atoms in T₁ is at least 25,

G_(x) is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight of branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 4 alkyl of 1 to 4 carbon atoms,

T₂ is straight or branched alkyl of 23 to 100 carbon atoms; and

with the proviso that at least one of E₁ and E₂ is a group—(CH₂)_(m)—CO—X—T₁ or a group —(CH₂)_(p)—X—CO—T₂, or at least one of G₂and G₂′ is a group —CO—G₃, —CO—G₃, —CO—NH—G₃, —CO—N(G₃)₂, —N(G₃)—CO—G₃,

where G₃ is T₁ or T₂.

It is understood that whether T₁ or T₂ is an alkyl group or a—(R—O)_(n)—R—OG_(x)group that such moieties are usually a mixture ofmolecular weights falling within the scope of the total number of atomsindicated.

When R is ethylene, the group T₁ is —(CH₂CH₂O)_(n)—CH₂CH₂OG_(x) where nis 12 to 49.

When R is propylene, the group T₁ is —(CH(CH₃)CH₂O)_(n)—CH(CH₃)CH₂OG_(x)where n is 8 to 32.

When R is trimethylene, the group T₁ is—(CH₂CH₂CH₂O)_(n)—CH₂CH₂CH₂OG_(x) where n is 8 to 32.

When R is tetramethylene, the group T₁ is—(CH₂CH₂CH₂CH₂O)_(n)—CH₂CH₂CH₂CH₂O G_(x) where n is 6 to 24. Also R isalso 1,2-butylene so that T₁ is—(CH(CH₂CH₃)CH₂O)_(n)—CH(CH₂CH₃)CH₂OG_(x) where n is 6 to 24.

The preferred embodiments of the compounds of formula I

are those where

G₁ is hydrogen,

G₂ is hydrogen, chloro, fluoro, cyano, E₃SO—, E₃SO₂—, —COOG₃, CF₃,—CO—G₃, —CO—NH—G₃ or —CO—N(G₃)₂,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight of branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atomsor phenyl; or G₃ is T₁ or T₂,

E₁ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight or branched chain alkenyl of 2 to 24 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atomsor phenyl; or E₁ is the group —(CH₂)_(m)—CO—X—T₁ where m is 0, 1 or 2;or E₁ is the group —(CH₂)_(p)—X—CO—T₂ where p is 1, 2 or 3,

E₂ is straight or branched alkyl chain of 1 to 24 carbon atoms, straightor branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms or phenyl; or E₂ issaid alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbonatoms substituted by one or more —OH, —OCOE₁₁, —OE₄, —NHCOE₁₁, —NHE₄ or—N(E₄)₂, or mixtures thereof, where E₄ is straight or branched chainalkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interruptedby one or more —O—, —NH— or —NE₄— groups or mixtures thereof and whichcan be unsubstituted or substituted by one or more —OH, —OE₄ or —NH₂groups or mixtures thereof; or E₄ is T₁ or T₂; or E₂ is—(CH₂)_(m)—CO—X—T₁ or —(CH₂)_(p)—X—CO—T₂,

X is —O— or —N(E₁₆)—,

E₁₆ is hydrogen,

E₁₁ is a straight or branched chain C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl,C₆-C₁₄aryl or C₇-C₁₅aralkyl; or E₁₁ is T₁ or T₂,

E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms or aryl of 6 to 10 carbon atoms,

T₁ is straight or branched chain alkyl of 25 to 70 carbon atoms, or saidalkyl substituted by one hydroxyl group and interrupted by one oxamoiety, or a mixture of such alkyl moieties; or

T₁ is —(R—O)_(n)—R—OH where R is ethylene, propylene, trimethylene ortetramethylene, and n is 6 to 49 so that the total number of carbonatoms in T₁ is at least 25, and

T₂ is straight or branched alkyl of 23 to 70 carbon atoms; and

with the proviso that at least one of E₁ and E₂ is a group—(CH₂)_(m)—CO—X—T₁ or a group —(CH₂)_(p)—X—CO—T₂, or at least one of G₂and G₂′is a group —COOG₃, —CO—G₃, —CO—NH—G₃, —CO—N(G₃)₂, —N(G₃)—CO—G₃,

where G₃ is T₁ or T₂.

The preferred embodiments of the compounds of formula III

wherein

G₁ and G_(1′) are hydrogen, G₂ and G₂′ are independently hydrogen,chloro, fluoro, cyano, E₃SO—, E₃SO₂—, —COOG₃, CF₃, —CO—G₃, —CO—NH—G₃ or—CO—N(G₃)₂,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight of branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atomsor phenyl; or G₃ is T₁ or T₂,

E₂ and E₂′ are independently straight or branched alkyl chain of 1 to 24carbon atoms, straight or branched chain alkenyl of 2 to 18 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms or phenyl; or E₂ and E₂′ are independently said alkyl of 1 to 24carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by oneor more —OH, —OCOE₁₁, —OE₄, —NHCOE₁₁, —NHE₄ or —N(E₄)₂, or mixturesthereof, where E₄ is straight or branched chain alkyl of 1 to 24 carbonatoms; or said alkyl or said alkenyl interrupted by one or more —O—,—NH— or —NE₄— groups or mixtures thereof and which can be unsubstitutedor substituted by one or more —OH, —OE₄ or —NH2 groups or mixturesthereof; or E₄ is T₁ or T₂; or E₂ and E₂′ are independently—(CH₂)_(m)—CO—X—T₁ or —(CH₂)_(p)—X—CO—T₂,

E₁₆ is hydrogen,

E₁₁ is a straight or branched chain C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl,C₆-C₁₄aryl or C₇-C₁₅aralkyl; or E₁₁ is T₁ or T₂,

E₃ is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbonatoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbonatoms or aryl of 6 to 10 carbon atoms,

L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbonatoms, benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylylene orcycloalkylidene,

T₁ is straight or branched chain alkyl of 25 to 70 carbon atoms, or saidalkyl substituted by one hydroxyl group and interrupted by one oxamoiety, or a mixture of such alkyl moieties; or

T₁ is —(R—O)_(n)—R—OH where R is ethylene, propylene, tnimethylene ortetramethylene, and n is 6 to 49 so that the total number of carbonatoms in T, is at least 25, and

T₂ is straight or branched alkyl of 23 to 70 carbon atoms; and

with the proviso that at least one of E₂ and E₂′ is a group—(CH₂)_(m)—CO—X—T₁ or a group —(CH₂)_(p)—X—CO—T₂, or at least one of G₂and G₂′ is a group —COOG₃, —CO—G₃, —CO—NH—G₃, —CO—N(G₃)₂, —N(G₃)—CO—G₃,

where G₃ is T₁ or T_(2.)

The instant invention also pertains to compositions stabilized againstthermal, oxidative or light-induced degradation which comprise

(a) an organic material subject to thermal, oxidative or light-induceddegradation, and

(b) an effective stabilizing amount of a compound of formula I, II orIII as described above.

In general polymers which can be stabilized include

1. Polymers of monoolefins and diolefins, for example polypropylene,polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene orpolybutadiene, as well as polymers of cycloolefins, for instance ofcyclopentene or norbornene, polyethylene (which optionally can becrosslinked), for example high density polyethylene (HDPE), low densitypolyethylene (LDPE), linear low density polyethylene (LLDPE), branchedlow density polyethylene (BLDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in thepreceding paragraph, preferably polyethylene and polypropylene, can beprepared by different, and especially by the following, methods:

a) radical polymerisation (normally under high pressure and at elevatedtemperature).

b) catalytic polymerisation using a catalyst that normally contains oneor more than one metal of groups IVb, Vb, VIb or VIII of the PeriodicTable. These metals usually have one or more than one ligand, typicallyoxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenylsand/or aryls that may be either π- or σ-coordinated. These metalcomplexes may be in the free form or fixed on substrates, typically onactivated magnesium chloride, titanium(III) chloride, alumina or siliconoxide. These catalysts may be soluble or insoluble in the polymerisationmedium. The catalysts can be used by themselves in the polymerisation orfurther activators may be used, typically metal alkyls, metal hydrides,metal alkyl halides, metal alkyl oxides or metal alkyloxanes, saidmetals being elements of groups Ia, IIa and/or IIIa of the PeriodicTable. The activators may be modified conveniently with further ester,ether, amine or silyl ether groups. These catalyst systems are usuallytermed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont),metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1), for example mixtures ofpolypropylene with polyisobutylene, polypropylene with polyethylene (forexample PP/HDPE, PP/LDPE) and mixtures of different types ofpolyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with othervinyl monomers, for example ethylene/propylene copolymers, linear lowdensity polyethylene (LLDPE) and mixtures thereof with low densitypolyethylene (LDPE), propylene/but-1-ene copolymers,propylene/isobutylene copolymers, ethylene/but-i -ene copolymers,ethylene/hexene copolymers, ethylene/methylpentene copolymers,ethylene/heptene copolymers, ethylene/octene copolymers,propylene/butadiene copolymers, isobutylene/-isoprene copolymers,ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylatecopolymers, ethylene/vinyl acetate copolymers and their copolymers withcarbon monoxide or ethylene/acrylic acid copolymers and their salts(ionomers) as well as terpolymers of ethylene with propylene and a dienesuch as hexadiene, dicyclopentadiene or ethylidene-norbornene; andmixtures of such copolymers with one another and with polymers mentionedin 1) above, for example polypropylene/ethylene-propylene copolymers,LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acidcopolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or randompolyalkylene/carbon monoxide copolymers and mixtures thereof with otherpolymers, for example polyamides.

4. Hydrocarbon resins (for example C₅-C₉) including hydrogenatedmodifications thereof (e.g. tackifiers) and mixtures of polyalkylenesand starch.

5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

6. Copolymers of styrene or α-methylstyrene with dienes or acrylicderivatives, for example styrene/butadiene, styrene/acrylonitrile,styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate,styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride,styrene/acrylonitrile/methyl acrylate; mixtures of high impact strengthof styrene copolymers and another polymer, for example a polyacrylate, adiene polymer or an ethylene/-propylene/diene terpolymer, and blockcopolymers of styrene such as styrene/butadiene/-styrene,styrene/isoprene/styrene, styrene/ethylene/butylene/styrene orstyrene/ethylene/-propylene/styrene.

7. Graft copolymers of styrene or a-methylstyrene, for example styreneon polybutadiene, styrene on polybutadiene-styrene orpolybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (ormethacrylonitrile) on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride onpolybutadiene; styrene, acrylonitrile and maleic anhydride or maleimideon polybutadiene; styrene and maleimide on polybutadiene; styrene andalkyl acrylates or methacrylates on polybutadiene; styrene andacrylonitrile on ethylene/propylene/diene terpolymers; styrene andacrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styreneand acrylonitrile on acrylate/butadiene copolymers, as well as mixturesthereof with the copolymers listed under 6), for example the copolymermixtures known as ABS, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinatedrubbers, chlorinated or sulfochlorinated polyethylene, copolymers ofethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers,especially polymers of halogen-containing vinyl compounds, for examplepolyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride,polyvinylidene fluoride, as well as copolymers thereof such as vinylchloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidenechloride/vinyl acetate copolymers.

9. Polymers derived from a,D-unsaturated acids and derivatives thereofsuch as polyacrylates and polymethacrylates; polymethyl methacrylates,polyacrylamides and polyacrylonitriles, impact-modified with butylacrylate.

10. Copolymers of the monomers mentioned under 9) with each other orwith other unsaturated monomers, for example acrylonitrile/butadienecopolymers, acrylonitrile/-alkyl acrylate copolymers,acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halidecopolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof, for example polyvinyl alcohol, polyvinylacetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate,polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well astheir copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkyleneglycols, polyethylene oxide, polypropylene oxide or copolymers thereofwith bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; polyacetals modified withthermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenyleneoxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers,polyesters or polybutadienes on the one hand and aliphatic or aromaticpolyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylicacids and/or from aminocarboxylic acids or the corresponding lactams,for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12,4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides startingfrom m-xylene diamine and adipic acid; polyamides prepared fromhexamethylenediamine and isophthalic or/and terephthalic acid and withor without an elastomer as modifier, for examplepoly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenyleneisophthalamide; and also block copolymers of the aforementionedpolyamides with polyolefins, olefin copolymers, ionomers or chemicallybonded or grafted elastomers; or with polyethers, e.g. with polyethyleneglycol, polypropylene glycol or polytetramethylene glycol; as well aspolyamides or copolyamides modified with EPDM or ABS; and polyamidescondensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or fromhydroxycarboxylic acids or the corresponding lactones, for examplepolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoates,as well as block copolyether esters derived from hydroxyl-terminatedpolyethers; and also polyesters modified with polycarbonates or MBS.

19. Polycarbonates and polyester carbonates.

20. Polysulfones, polyether sulfones and polyether ketones.

21. Crosslinked polymers derived from aldehydes on the one hand andphenols, ureas and melamines on the other hand, such asphenolformaldehyde resins, urea/formaldehyde resins andmelaminelformaldehyde resins.

22. Drying and non-drying alkyd resins.

23. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents, and also halogen-containingmodifications thereof of low flammability.

24. Crosslinkable acrylic resins derived from substituted acrylates, forexample epoxy acrylates, urethane acrylates or polyester acrylates.

25. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, polyisocyanates or epoxy resins.

26. Crosslinked epoxy resins derived from polyepoxides, for example frombisglycidyl ethers or from cycloaliphatic diepoxides.

27. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, for example cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose; as well as rosins and their derivatives.

28. Blends of the aforementioned polymers (polyblends), for examplePP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS,PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR,PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 andcopolymers, PA/HDPE, PA/PP, PA/PPO.

29. Naturally occurring and synthetic organic materials which are puremonomeric compounds or mixtures of such compounds, for example mineraloils, animal and vegetable fats, oil and waxes, or oils, fats and waxesbased on synthetic esters (e.g. phthalates, adipates, phosphates ortrimellitates) and also mixtures of synthetic esters with mineral oilsin any weight ratios, typically those used as spinning compositions, aswell as aqueous emulsions of such materials.

30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latexor latices of carboxylated styrene/butadiene copolymers.

31. Polysiloxanes such as the soft, hydrophilic polysiloxanes described,for example, in U.S. Pat. No. 4,259,467; and the hardpolyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

32. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins. Theunsaturated acrylic resins include the urethane acrylates, polyetheracrylates, vinyl or acryl copolymers with pendant unsaturated groups andthe acrylated melamines. The polyketimines are prepared from polyaminesand ketones in the presence of an acid catalyst.

33. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

34. Epoxymelamine resins such as light-stable epoxy resins crosslinkedby an epoxy functional coetherified high solids melamine resin such asLSE₄₁₀₃ (Monsanto).

In general, the compounds of the present invention are employed in fromabout 0.01 to about 5% by weight of the stabilized composition, althoughthis will vary with the particular substrate and application. Anadvantageous range is from about 0.05 to about 3%, and especially 0.05to about 2%. However, some high performance films or in UV absorbinglayers of laminates such as those produced by coextrusion may containfrom 5-15% by weight of the instant compounds. Concentrations of 5-10%by weight are typical in certain coextrusion applications.

The stabilizers of the instant invention may readily be incorporatedinto the organic polymers by conventional techniques, at any convenientstage prior to the manufacture of shaped articles therefrom. Forexample, the stabilizer may be mixed with the polymer in dry powderform, or a suspension or emulsion of the stabilizer may be mixed with asolution, suspension, or emulsion of the polymer. The resultingstabilized polymer compositions of the invention may optionally alsocontain from about 0.01 to about 10%, preferably from about 0.025 toabout 2%, and especially from about 0.1 to about 2% by weight of variousconventional additives, such as the materials listed below, or mixturesthereof.

1. Antioxidants

1.1. Alkylated monophenols, for example,

2,6-di-tert-butyl-4-methylphenol

2-tert-butyl-4,6-dimethylphenol

2,6-di-tert-butyl-4-ethylphenol

2,6-di-tert-butyl-4-n-butylphenol

2,6-di-tert-butyl-4-i-butylphenol

2,6-di-cyclopentyl-4-methylphenol

2-(α-methylcyclohexyl)-4,6-dimethylphenol

2,6-di-octadecyl-4-methylphenol

2,4,6-tri-cyclohexylphenol

2,6-di-tert-butyl-4-methoxymethylphenol

1.2. Alkylated hydroguinones, for example,

2,6-di-tert-butyl-4-methoxyphenol

2,5-di-tert-butyl-hydroquinone

2,5-di-tert-amyl-hydroquinone

2,6-diphenyl-4-octadecyloxyphenol

1.3. Hydroxylated thiodiphenyl ethers, for example,

2,2′-thio-bis-(6-tert-butyl-4-methylphenol)

2,2′-thio-bis-(4-octylphenol)

4,4′-thio-bis-(6-tert-butyl-3-methylphenol)

4,4′-thio-bis-(6-tert-butyl-2-methylphenol)

1.4. Alkylidene-bisphenols, for example,

2,2′-methylene-bis-(6-tert-butyl-4-methylphenol)

2,2′-methylene-bis-(6-tert-butyl-4-ethylphenol)

2,2′-methylene-bis-[4-methyl-6-(α-methylcyclohexyl)-phenol]

2,2′-methylene-bis-(4-methyl-6-cyclohexylphenol)

2,2 ′-methylene-bis-(6-nonyl-4-methylphenol)

2,2′-methylene-bis-[6-(α-methylbenzyl)-4-nonylphenol]

2,2′-methylene-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]

2,2 ′-methylene-bis-(4,6-di-tert-butylphenol)

2,2′-ethylidene-bis-(4,6-di-tert-butylphenol)

2,2′-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)

4,4′-methylene-bis-(2,6-di-tert-butylphenol)

4,4′-methylene-bis-(6-tert-butyl-2-methylphenol)

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

2,6di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol

1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane

1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane

ethyleneglycol bis-[3,3-bis-(3′-tert-butyl-4′-hydroxyphenyl)-butyrate]

di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene

di-[2-(3′-tert-butyl-2′-hydroxy-5′-methyl-benzyl)-6-tert-butyl-4-methylphenyl]terephthalate.

1.5. Benzyl compounds, for example,

1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene

di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide

3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester

bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate

1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate

1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester

3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester,calcium-salt

1.6. Acylaminophenols, for example,

4-hydroxy-lauric acid anilide

4-hydroxy-stearic acid anilide

2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine

octyl—N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate

1.7. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid withmonohydric or polyhydric alcohols, for example,

methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

1.8. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acidwith monohydric or polyhydric alcohols, for example,

methanol diethylene glycol octadecanol triethylene glycol 1,6-hexanediolpentaerythritol neopentyl glycol tris-hydroxyethyl isocyanuratethiodiethylene glycol di-hydroxyethyl oxalic acid diamidetriethanolamine triisopropanolamine

1.9. Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid forexample,

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylenediamine

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenediamine

N,N′-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine

1.10 Diarylamines, for example,

diphenylamine, N-phenyl-1-naphthylamine,N-(4-tert-octylphenyl)-1-naphthylamine,

4,4′-di-tert-octyl-diphenylamine, reaction product ofN-phenylbenzylamine and

2,4,4-trimethylpentene, reaction product of diphenylamine and2,4,4-trimethylpentene, reaction product of N-phenyl-1-naphthylamine and2,4,4-trimethylpentene.

2. UV Absorbers and Light Stabilizers

2.1. 2-(2′-Hydroxyphenyl)-benzotriazoles, for example, the 5′-methyl-,3′, 5′-di-tert-butyl-, 5′-tert-butyl-, 5′-(1,1,3,3-tetramethylbutyl)-,5-chloro-3′, 5′-di-tert-butyl-, 5-chloro-3′-tert-butyl-5′-methyl-,3′-sec-butyl-5′-tert-butyl-, 4′-octoxy, 3′, 5′-di-tert-amyl-, 3′,5′-bis-(α,α-dimethylbenzyl),3′-tert-butyl-5′-(2-(omega-hydroxy-octa-(ethyleneoxy)carbonyl-ethyl)-,3′-dodecyl-5′-methyl-, and 3′-tert-butyl-5′-(2-octyloxycarbonyl)ethyl-,and dodecylated-5′-methyl derivatives.

2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy, 4,2′, 4′-trihydroxy-and 2′-hydroxy-4,4′-dimethoxy derivatives.

2.3. Esters of optionally substituted benzoic acids for example, phenylsalicylate, 4-tert-butylphenyl salicylate, octylphenyl salicylate,dibenzoylresorcinol, bis-(4-tertbutylbenzoyl)-resorcinol,benzoylresorcinol, 3,5-di-tert-butyl-4-hydroxybenzoic acid2,4-di-tert-butylphenyl ester and 3,5-di-tert-butyl-4-hydroxybenzoicacid hexadecyl ester.

2.4. Acrylates, for example, α-cyano-β,β-diphenylacrylic acid ethylester or isooctyl ester, (α-carbomethoxy-cinnamic acid methyl ester,α-cyano-β-methyl-p-methoxy-cinnamic acid methyl ester or butyl ester,α-carbomethoxy-β-methoxy-cinnamic acid methyl ester,N-(β-carbomethoxy-β-cyanovinyl)-2-methyl-indoline.

2.5. Nickel compounds, for example, nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or1:2 complex, optionally with additional ligands such as n-butylamine,triethanolamine or N-cyclohexyl-diethanolamine, nickeldibutyldithiocarbamate, nickel salts of4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters, suchas of the methyl, ethyl or butyl ester, nickel complexes of ketoximessuch as of 2-hydroxy-4-methyl-phenyl undecyl ketoxime, nickel complexesof 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additionalligands.

2.6. Sterically hindered amines, for examplebis-(2,2,6,6-tetramethylpiperidyl) sebacate,bis-(1,2,2,6,6-pentamethylpiperidyl) sebacate,n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acidbis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product of1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, condensation product ofN,N′-(2,2,6,6-tetramethylpiperidyl)-hexamethylenediamine and4-tert-octylamino-2,6-dichloro-s-triazine,tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate,1,1′(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine.

2.7. Oxalic acid diamides, for example, 4,4′-di-octyloxy-oxanilide,2,2′-di-octyloxy-5,5′-di-tert-butyl-oxanilide,2,2′-di-dodecyloxy-5,5′-di-tert-butyl-oxanilide,2-ethoxy-2′-ethyl-oxanilide, N,N′-bis (3-dimethylaminopropyl)-oxalamide,2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butyloxanilide and mixtures of ortho- andpara-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilides.

2.8. Hydroxyphenyl-s-triazines, for example2,6-bis-(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;2,6-bis-(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine;2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydroxyethoxy)phenyl]-6-(2,4-dimethylphenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]-6-(4-bromophenyl)-s-triazine;2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chlorophenyl)-s-triazine,2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine,2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-5-α-cumylphenyl)-s-triazine.

3. Metal deactivators, for example, N,N′-diphenyloxalic acid diamide,N-salicylal—N′-salicyloylhydrazine, N,N′-bis-salicyloylhydrazine,N,N′-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic aciddihydrazide.

4. Phosphites and phosphonites, for example, triphenyl phosphite,diphenylalkyl phosphites, phenyldialkyl phosphites, tri-(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite,di-stearyl-pentaerythritol diphosphite, tris-(2,4-di-tert-butylphenyl)phosphite, di-isodecylpentaerythritol diphosphite,di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,tristearyl-sorbitol triphosphite, tetrakis-(2,4-di-tert-butylphenyl)4,4′-diphenylylenediphosphonite.

5. Compounds which destroy peroxide, for example, esters of,-thiodipropionic acid, for example the lauryl, stearyl, myristyl ortridecyl esters, mercapto-benzimidazole or the zinc salt of2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate, dioctadecyldisulfide, pentaerythritol tetrakis-(β-dodecylmercapto)-propionate.

6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,N-hexadecyl-N-octadecylhydroxylamine,N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derivedfrom hydrogenated tallow amine.

7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl nitrone,N-hexadecyl-alpha-pentadecyl nitrone,N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alphaheptadecylnitrone, N-octadecyl-alpha-pentadecyl nitrone,N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxylamine derived fromhydrogenated tallow amine.

8. Polyamide stabilizers, for example copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

9. Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone,dicyandiamide, triallyl cyanurate, urea derivatives, hydrazinederivatives, amines, polyamides, polyurethanes, alkali metal salts andalkaline earth metal salts of higher fatty acids for example Castearate, Zn stearate, Mg stearate, Na ricinoleate and K palmitate,antimony pyrocatecholate or zinc pyrocatecholate.

10. Nucleating agents, for example, 4-tert-butyl-benzoic acid, adipicacid, diphenylacetic acid.

11. Fillers and reinforcing agents, for example, calcium carbonate,silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate,metal oxides and hydroxides, carbon black, graphite.

12. Other additives, for example, plasticizers, lubricants, emulsifiers,pigments, optical brighteners, flameproofing agents, anti-static agents,blowing agents and thiosynergists such as dilauryl thiodipropionate ordistearyl thiodipropionate.

13. Benzofuranones and indolinones, for example those disclosed in U.S.Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312,or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one,5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one],5,7-di-tert-butyl-3-(4-ethoxyphenyl)-benzofuran-2-one,3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,3-(3,5-di-methyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

14. Amine Oxides, for example amine oxide derivatives as disclosed inU.S. Pat. Nos. 5,844,029 and 5,880,191, e.g. didecyl methyl amine oxide,tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amineoxide.

The co-stabilizers, with the exception of the benzofuranones listedunder 13, are added for example in concentrations of 0.01 to 10%,relative to the total weight of the material to be stabilized.

Further preferred compositions comprise, in addition to components (a)and (b) further additives, in particular phenolic antioxidants, lightstabilizers or processing stabilizers.

Particularly preferred additives are phenolic antioxidants (item 1 ofthe list), sterically hindered amines (item 2.6 of the list), phosphitesand phosphonites (item 4 of the list), UV absorbers (item 2 of the list)and peroxide-destroying compounds (item 5 of the list).

Additional additives (stabilizers) which are also particularly preferredare benzofuran-2-ones, such as described, for example, in U.S. Pat. No.4,325,863, U.S. Pat. No. 4,338,244 or U.S. Pat. No. 5,175,312.

The phenolic antioxidant of particular interest is selected from thegroup consisting of

n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,

neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate),

di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,

1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,

thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),

1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,

3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),

2,6-di-tert-butyl-p-cresol,

2,2′-ethylidene-bis(4,6-di-tert-butylphenol),

1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocynurate,

1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,

1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate,

3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol,

hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),

1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine,

N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),

calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),

ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate],

octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,

bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and

N,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]oxamide.

A most preferred phenolic antioxidant is neopentanetetrayltetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl3,5-di-tert-butyl-4-hydroxyhydrocinnamate,1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,2,6-di-tert-butyl-p-cresol or2,2′-ethylidene-bis(4,6-di-tert-butylphenol).

The hindered amine compound of particular interest is selected from thegroup consisting of

bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,

di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate,

4-benzoyl-2,2,6,6-tetramethylpiperidine,4-stearyloxy-2,2,6,6-tetramethylpiperidine,

3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione,

tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate,

1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin-4-yl)ethane,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),polycondensation product of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid, polycondensation product of4,4′-hexamethylenebis-(amino-2,2,6,6-tetra-methylpiperidine) and1,2-dibromoethane,

tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,

tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl)1,2,3,4-butanetetracarboxylate,

polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and

4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N″′-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane,mixed

[2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane) diethyl] 1,2,3,4-butanetetracarboxylate,

mixed[1,2,2,6,6-pentamethylpiperidin4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane)diethyl]1,2,3,4-butanetetracarboxylate, octamethylenebis(2,2,6,6-tetramethylpiperidin-4-carboxylate),

4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one),N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide,N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine;1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine;2-(2-hydroxyethylamino)-4,6-bis[N-butyl—N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-s-triazine; 1,3,5-tris{N-cyclohexyl—N-[2-(3,3,5,5-tetramethylpiperazin-2-on-1-yl)ethyl]amino}-s-triazine;and 1,3,5-tris{N-cyclohexyl—N-[2-(3,3,4,5,5-pentamethylpiperazin-2-on-1-yl)ethyl]amino}-s-triazine.

A most preferred hindered amine compound isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N″′-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane.di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidineor2-(2-hydroxyethylamino)-4,6-bis[N-butyl—N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-s-triazine.

The instant composition can additionally contain another UV absorberselected from the group consisting of the benzotriazoles, thes-triazines, the oxanilides, the hydroxybenzophenones, the malonates,the salicylates, the benzoates and the α-cyanoacrylates.

Particularly, the instant composition may additionally contain aneffective stabilizing amount of at least one other2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; orhindered amine or mixtures thereof.

Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected from thegroup consisting of

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;

5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;

2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; and

2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.

Preferably, the other tris-aryl-s-triazine is selected from the groupconsisting of

2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;

2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;

2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine;and

2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxy-propoxy)-5-α-cumylphenyl]-s-triazine.

The organic material is preferably a natural, semi-synthetic orsynthetic polymer, and preferably is a polyolefin, especiallypolyethylene or polypropylene. Most preferably, the polyolefin is lowdensity polyethylene (LDPE).

One objective of this invention is to provide new benzotriazole UVabsorbers which are non-blooming at high concentrations in polyolefins,absorb more than 90% of UV light, especially in the near visible rangejust below 400 nm. The areas where the instant benzotriazoles will findgreat utility include packaging films, solar control films, opticalfilms, food wrap, medical packaging and the like. Non-blooming,non-migrating UV absorbers are particularly needed for the foodpackaging applications.

This includes the use of the instant compounds in rigid or flexiblemono- and/or multi-layered packaging materials such as poly(ethyleneterephthalate), polyethylene or polypropylene bottles. Such bottles areused for various items such as foods, food oils, vitamins, milk,beverages and beer which materials may have light sensitivity where thepresence of the UV absorber in the bottle itself can provide desirableprotection not only to the bottle itself, but also to its contents. Insuch situations, the resistance of the instant compounds to blooming orto migration is highly desirable.

The instant compounds, having a long chain hydrocarbyl moiety presentwhich exhibit excellent compatibility with hydrocarbon waxes such asthose used for candles, provide excellent light stability protection towhite, dipped, dyed, unscented and/or scented candles.

The instant compounds also are effective stabilizers for a polymer whichis a polyolefin, polycarbonate, a styrenic, ABS, a nylon (polyamide), apolyester, a polyurethane, a polyacrylate, a rubber modified styrenic,poly(vinyl chloride), poly(vinyl butyral), polyacetal(polyoxymethylene), or other blends or copolymers such aspoly(ethylene/1,4-cyclohexylene-dimethylene terephthalate) PETG or anethylene/acrylic acid copolymer or salts thereof (an ionomer).

Preferably, the polymer is a polyester; such as poly(ethyleneterephthalate), poly(butylene terephthalate) or poly(ethylenenaphthalenedicarboxylate), or copolymerpoly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETG.

Another class of polymers include the thermoplastic polymers such as thepolyolefins and polycarbonates.

The stabilized compositions may additionally contains an effectivestabilizing amount of at least one other UV absorber selected from thegroup consisting the benzotriazoles, the s-triazines, thehydroxy-benzophenones, the α-cyanoacrylates, the oxanilides, themalonates, the salicylates and the benzoates.

The compositions preferably contain an additional2-hydroxyphenyl-2H-benzotriazole is selected from the group consistingof

2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole;

2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole;

2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;

2-(2-hydroxy-3-sec -butyl-5-tert-butylphenyl)-2H-benzotriazole;

2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole;

2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;and

2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.

Preferably the other benzotriazole is

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole;

2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;

5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;

2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; or

2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.

The instant compositions may also contain an effective amount of ahindered amine.

The instant invention also pertains to candle wax compositions whichcomprises

(a) candle wax which is white and unscented; white and scented; dyed andunscented; dyed and scented; dipped and unscented; or dipped andscented, and

(b) an effective stabilizing amount of a benzotriazole of formula I, IIor III as described above alone or in combination with a hindered amine.

An effective amount of benzotriazole alone or plus the hindered amine inthe candle wax is 0.01 to 10% by weight, preferably 0.1 to 2% by weight;and most preferably 0.1 to 0.5% by weight based on the wax. When acombination of benzotriazole and hindered amine are used, the weightratio of benzotriazole to hindered amine is 10:1 to 1:10; preferably 4:1to 1:4; most preferably 2:1 to 1:2 based on the candle wax.

It should be noted that candles contain a host of various components.The base materials may be made up of the following:

paraffin wax,

natural oils,

polyamide plus fatty acid/ester,

fatty acids such as stearin,

opacifiers,

beeswax,

glycerides plus oxidized wax,

alcohols, and

ethylene oligomers.

Candles also contain a number of additives such as the following:

mold release agents,

fragrances,

insect repellants or insecticides,

hardeners,

crystal modifiers,

clarifiers,

guttering reducers,

colorants,

f.p. control agents,

stretchability improvers,

gelling agents,

extrusion aids, and

vortex reducers.

Each of the various components are meant to control or modify theproperties of the candle to insure proper burning, reduce channelling,aid in uniform melting, and the like. The colorants and fragrancesobviously are there to provide the proper color, scent or otheraesthetic appeal.

Of increasing importance are the transparent gel candles which look likeclear glass, but which burn like a classical candle. As is discussed indetail in U.S. Pat. No. 5,879,694, the relevant parts of which areincorporated herein by reference, these gel candles usually contain acopolymer selected from the group consisting of a triblock, radialblock, diblock or multiblock copolymer classically made up of at leasttwo thermodynamically incompatible segments containing both hard andsoft segments. Typical of such block copolymers is KRATON® (ShellChemical Co.) which consists of block segments of styrene monomer unitsand rubber monomer or comonomer units. The most common structure foundin KRATON® D series is a linear ABA block with styrene-butadiene-styrene(SBS) or styrene-isoprene-styrene (SIS).

Candles may also contain other stabilizers such as phenolicantioxidants, phosphites, long chain N,N-dialkylhydroxylamines,nitrones, amine oxides and the like, particularly phenolic antioxidantssuch as are described above.

The following examples are for illustrative purposes only and are not tobe construed to limit the scope of the instant invention in any mannerwhatsoever.

Examples 1-5 describe typical synthetic examples of the instantinvention. Example 6 is a comparative example. Example 7 denotes thepreparation of a low density polyethylene (LDPE) film in which areincorporated commercial and experimental UV absorbers.

Examples 8-19 provides the results of UV absorber migration from thefilms prepared in Example 7. Migration is a measure of whether the UVabsorber will bloom from the polyolefin composition.

Examples 104-113 show the use of these long chain benzotriazoles inpreventing color fade in various candle wax formulations.

Raw Materials

Polyethylene monoalcohol(s), both average molecular weights of 460 andof 700, are obtained from the Aldrich Chemical Company. Polyethylenepowder (640 I) is obtained from the Dow Chemical Company. All otherreagents and solvents are obtained from commercial sources.

The commercial UV absorbers used for comparisons are all provided by theCiba Specialty Chemicals Company as:

TINUVIN®326-5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;designated in the Examples as Example A;

TINUVIN®327-5-chloro-2-(2-bydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;designated in the Examples as Example B;

TINUVIN®360-2,2′-methylene-bis[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol];designated in the Examples as Example C;

TINUVIN® 1577-2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;designated in the Examples as Example D; and

Example E—methyl3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate.

Raw Materials for Candle Wax

Fully refined wax with a melting point of 137-141° C. and <0.5% oilcontent is obtained from the Astor Wax Company.

Dyes are supplied by French Color and Chemical Corporation.

Additional wax samples are supplied by the Candle Corporation ofAmerica. These samples contained red, green or yellow dyes andfragrances. Still other wax samples are supplied by the Candle-LiteCorporation which contain gray, green or blue dyes and fragrances.

The UV absorbers and hindered amine stabilizers are obtained from theCiba Speciality Chemicals Corporation.

Sample Preparation

The wax samples obtained from the Candle-Lite Corporation alreadycontain a dye and a fragrance (scent). In these cases, the wax is meltedand the appropriate stabilizer(s) is (are) added and dissolved in themolten wax. The stabilized wax is then poured into a mold(7″×8.5″×0.25″; 17.78 cm×21.59 cm×0.635 cm) giving a wax plaque.

To the wax samples obtained from the Astor Wax Company after melting areadded 0.001% by weight of the test dyes to give a dyed candle wax base.To the dyed wax base after melting is (are) added the appropriatestabilizer(s). The melted stabilized and dyed wax is then poured intothe mold described above to give a wax plaque.

Sample Exposure

The wax plaques described above are cut into eight equal pieces(3.5″×2.125″; 8.89 cm×5.40 cm). Triplicate samples of each are exposedunder a bank of six (6) cool-white fluorescent lamps (40 watts) or undera bank of six (6) UV lamps having a wavelength of 368 nm with the testsamples being twelve (12) inches (30.48 cm) below the lamps.

Dye color fade (or color change) is measured by a Macbeth ColorEyeSpectrophotometer with a 6 inch integrating sphere. The conditions are:10 degree observer, D65 illuminant and 8 degree viewing angle.

Initial color measurements are taken using the above parameters. The L,a and b values are calculated using the CIE system from the reflectancevalues. YI is calculated from the L, a and b values. Subsequentmeasurements are taken at specified intervals. Delta L, a, b and YIvalues are simply the difference between the initial values and thevalues at each interval. Delta(Δ) E is calculated as follows:

[(Delta L)²+(Delta a)²+(Delta b)²]^(½)= Delta E.

EXAMPLE 1 C₂₀-C₄₀Alkyl3-(2H-Benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

3-(2H-Benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid (70 g,0.206 mol), toluene (500 g, 5.38 mol), p-toluenesulfonic acid hydrate(3.2 g, 0.017 mol) and polyethylene monoalcohol (111.7 g, 0.206 mol,average molecular weight of 460) are charged to a laboratory reactor andthe contents are heated to reflux. The reaction mixture is refluxed forsix hours using a Dean-Stark trap to receive water, after which 5 g ofcarbon is added. Heating is continued for another two hours. The carbonis removed by filtration and the toluene solution is passed through abed of silica gel. The toluene is removed by distillation to yield 135 gof a light yellow oil which solidified on cooling. The desired productis obtained in two forms, one melting at 35-51° C. and the secondmelting at 58-63° C.

The polyethylene monoalcohol with an average molecular weight of 460 hasa nominal formula which may be written as CH₃(CH₂CH₂)_(n)CH₂OH where nis 9 to 19. The alkyl group in the title compound is a mixture of alkylmoieties ranging from eicosyl (C₂₀) to tetracontanyl (C₄₀) groups.

Analysis of the product:

¹Hnmr (CDCl₃) δ 0.89 (t, 3H), 1.10-1.40 (complex, 34-74H), 1.51 (s, 9H),1.62 (m, 2H), 2.70 (t, 2H), 3.01 (t, 2H), 4.09 (t, 2H), 7.22 (d, 1H),7.49 (complex, 2H), 7.94 (complex, 2H), 8.16 (d, 1H), 11.82 (s, 1H).

EXAMPLE 2 C₂₀-C₄₀Alkyl3-(5-Chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

Following the general procedure of Example 1, an equivalent amount of3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamicacid is substituted for3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid togive a 76.5% yield of the title compound as a light yellow solid whichhas two forms, one melting at 33° C. and the second melting at 57-67° C.

The title compound is a mixture of alkyl moieties as described inExample 1.

Analysis of the Product: ¹Hnmr (CDCl₃) δ 0.89 (t, 3H), 1.20-1.35(complex, 34-74H), 1.50 (s, 9H), 1.61 (m, 2H), 2.69 (t, 2H), 3.00 (t,2H), 4.09 (t, 2H), 7.23 (d, 1H), 7.44 (dd, 1H), 7.88 (d, 1H), 7.93 (d,1H), 8.12 (d, 1H), 11.58 (s, 1H).

EXAMPLE 3 C20-C₄₀Alkyl3-(5-Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

Following the general procedure of Example 1, an equivalent amount of3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamicacid is substituted for3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid togive a 82.5% yield of the title compound as a light yellow solid whichmelts at 60-66° C.

The title compound is a mixture of alkyl moieties as described inExample 1.

Analysis of the Product:

¹Hnmr (CDCl₃) δ 0.89 (t, 3H), 1.10-1.40 (complex, 34-74H), 1.51 (s, 9H),1.62 (m, 2H), 2.70 (t, 2H), 3.02 (t, 2H), 4.09 (t, 2H), 7.26 (d, 1H),7.69 (dd, 1H), 8.07 (d, 1H), 8.17 (d, 1H), 8.30 (d, 1H), 11.55 (s, 1H).

¹⁹Fnmr: singlet at −68.9 ppm.

EXAMPLE 4 C₂₀-C₄₀Alkyl3-(5-Phenylsulfonyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

Following the general procedure of Example 1, an equivalent amount of3-(5-phenylsulfonyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamicacid is substituted for3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid togive a 70.3% yield of the title compound as a light yellow solid whichhas two forms, one melting at 42° C. and the second melting at 65-74° C.

The title compound is a mixture of alkyl moieties as described inExample 1.

Analysis of the Product:

¹Hnmr (CDCl₃) δ 0.89 (t, 3H), 1.20-1.34 (complex 34-74H), 1.49 (s, 9H),1.62 (m, 2H), 2.69 (t, 2H), 3.00 (t, 2H), 4.09 (t, 2H), 7.26 (d, 1H),7.55 (t, 2H), 7.61 (t, 1H), 8.03 (d, 2H), 8.03 (d, 1H), 8.72 (d, 1H),11.45 (s, 1H).

EXAMPLE 5 C₄₀-C₆₀Alkyl3-(2H-Benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

Methyl 3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate(35.3 g, 0.1 mol), polyethylene monoalcohol (70 g, 0.1 mol, averagemolecular weight of 700) and lithium amide (0.7 g, 0.01 mol) are chargedto a reaction flask and the contents are heated to 140° C. The reactionmixture is kept at this temperature for 5.5 hours, acidified and thesolid formed is removed by filtration. The filter cake is washed withxylenes and dried to afford a light yellow solid which melts at 71-93°C.

The polyethylene monoalcohol with an average molecular weight of 700 hasa nominal formula which may be written as CH₃(CH₂CH₂)_(n)CH₂OH where nis 19 to 29. The alkyl group in the title compound is a mixture of alkylmoieties ranging from tetracontanyl (C₄₀) to hexacontanyl (C₆₀) groups.

Analysis of the Product:

¹Hnmr (CDCl₃) δ 0.89 (t, 3H), 1.10-1.44 (complex, 82-142H), 1.51 (s,9H), 1.61 (m, 2H), 2.70 (t, 2H), 3.01 (t, 2H), 4.10 (t, 2H), 7.23 (d,1H), 7.48 (complex, 2H), 7.94 (complex, 2H), 8.16 (d, 1H), 11.76 (s,1H).

EXAMPLE 6 Octadecyl3-(2H-Benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

In this comparative Example, using the general procedure of Example 5,an equivalent amount of n-octadecanol is used in place of thepolyethylene monoalcohol to give the title compound in a yield of 82%.

Analysis of the Product:

¹Hnmr (CDCl₃) δ 0.89 (t, 3H), 1.20-1.34 (complex, 30H), 1.51 (s, 9H),1.62 (m, 2H), 2.70 (t, 2H), 3.01 (t, 2H), 4.09 (t, 2H), 7.22 (d, 1H),7.49 (complex, 2H), 7.94 (complex, 2H), 8.16 (d, 1H), 11.81 (broadsinglet, 1H).

EXAMPLE 7 Preparation of LDPE films for UV Absorber Migration Values

Ground low density polyethylene powder (Dow 640 I) is tumble blendedwith the desired quantity of test UV absorber and 0.30% by weight ofSuperfloss antiblock agent. The blended resin is twin-screw compoundedat 450° F. (232° C.). The resulting pellets are blown at 400° F. (204°C.) into a monolayer film of approximately 3 mil thickness.

Blown films are used to study the migration of the test UV absorber fromthe interior of the film to the film surface. Additives that migratetend to produce a white deposit on the film surface which can be easilyscraped off. This is the phenomenon called blooming. It is clear that,if the additive blooms on to the surface of the film and is easilyremoved therefrom, it cannot serve to protect the film itself which isits purpose.

Visual assessment of the film surface is performed at approximately 30day intervals up to 375 days. The films are stored at room temperature.

EXAMPLE 8

The test UV absorbers are present at a 0.2% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 122 days. The films are observed after 0, 10, 30, 60 and 122 days.

blooming after days* UV absorber of 0 10 30 60 122 C no no yes yes yes Dno no yes yes yes E no no yes yes yes Example 6 no no no no no Example 1no no no no no Example 5 no no no no no *yes means a white deposit isclearly observed on the film surface indicating that migration orblooming has occurred. no means that no migration or blooming isobserved.

EXAMPLE 9

The test UV absorbers are present at a 0.2% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 375 days. The films are observed after 152, 182, 211, 255 and 375days.

blooming after days* UV absorber of 152 182 211 255 375 C yes yes yesyes yes D yes yes yes yes yes E yes yes yes yes yes Example 6 no no nono no Example 1 no no no no no Example 5 no no no no no *yes means awhite deposit is clearly observed on the film surface indicating thatmigration or blooming has occurred. no means that no migration orblooming is observed.

EXAMPLE 10

The test UV absorbers are present at a 0.4% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 122 days. The films are observed after 0, 10, 30, 60 and 122 days.

blooming after days* UV absorber of 0 10 30 60 122 A no no no no yes Cno no no yes yes D no no yes yes yes E no no yes yes yes Example 6 no nono no yes Example 1 no no no no no Example 5 no no no no no *yes means awhite deposit is clearly observed on the film surface indicating thatmigration or blooming has occurred. no means that no migration orblooming is observed.

EXAMPLE 11

The test UV absorbers are present at a 0.4% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 375 days. The films are observed after 152, 182, 211, 255 and 375days.

blooming after days* UV absorber of 152 182 211 255 375 A yes yes yesyes yes C yes yes yes yes yes D yes yes yes yes yes E yes yes yes yesyes Example 6 yes yes yes yes yes Example 1 no no no no no Example 5 nono no no no *yes means a white deposit is clearly observed on the filmsurface indicating that migration or blooming has occurred. no meansthat no migration or blooming is observed.

EXAMPLE 12

The test UV absorbers are present at a 0.8% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 122 days. The films are observed after 0, 10. 30. 60 and 122 days.

blooming after days* UV absorber of 0 10 30 60 122 A — — — — yes B — — —— yes E no yes yes yes yes Example 6 no no yes yes yes Example 1 no nono no no Example 5 no no no no no *yes means a white deposit is clearlyobserved on the film surface indicating that migration or blooming hasoccurred. no means that no migration or blooming is observed. — means noreading was taken during this interval.

EXAMPLE 13

The test UV absorbers are present at a 0.8% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 375 days. The films are observed after 152, 182, 211, 255 and 375days.

blooming after days* UV absorber of 152 182 211 255 375 A yes yes yesyes yes B yes yes yes yes yes E yes yes yes yes yes Example 6 yes yesyes yes yes Example 1 no no no no no Example 5 no no no no no *yes meansa white deposit is clearly observed on the film surface indicating thatmigration or blooming has occurred. no means that no migration orblooming is observed.

EXAMPLE 14

The test UV absorbers are present at a 1.2% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 122 days. The films are observed after 0, 10, 30, 60 and 122 days.

blooming after days* UV absorber of 0 10 30 60 122 Example 1 no no no nono Example 5 no no no no no *yes means a white deposit is clearlyobserved on the film surface indicating that migration or blooming hasoccurred. no means that no migration or blooming is observed.

EXAMPLE 15

The test UV absorbers are present at a 1.2% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 375 days. The films are observed after 152, 182, 211, 255 and 375days.

blooming after days* UV absorber of 152 182 211 255 375 Example 1 no nono no no Example 5 no no no no no *yes means a white deposit is clearlyobserved on the film surface indicating that migration or blooming hasoccurred. no means that no migration or blooming is observed.

EXAMPLE 16

The test UV absorbers are present at a 1.6% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 122 days. The films are observed after 0, 10, 30, 60 and 122 days.

blooming after days* UV absorber of 0 10 30 60 122 Example 1 no no no nono Example 5 no no no no no *yes means a white deposit is clearlyobserved on the film surface indicating that migration or blooming hasoccurred. no means that no migration or blooming is observed.

EXAMPLE 17

The test UV absorbers are present at a 1.6% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 375 days. The films are observed after 152, 182, 211, 255 and 375days.

blooming after days* UV absorber of 152 182 211 255 375 Example 1 no nono no no Example 5 no no no no no *yes means a white deposit is clearlyobserved on the film surface indicating that migration or blooming hasoccurred. no means that no migration or blooming is observed.

EXAMPLE 18

The test UV absorbers are present at a 2.0% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 122 days. The films are observed after 0, 10, 30, 60 and 122 days.

blooming after days* UV absorber of 0 10 30 60 122 Example 1 no no no nono Example 5 no no no no no *yes means a white deposit is clearlyobserved on the film surface indicating that migration or blooming hasoccurred. no means that no migration or blooming is observed.

EXAMPLE 19

The test UV absorbers are present at a 2.0% by weight concentration inthe 3 mil LDPE films prepared in Example 7 and held at room temperaturefor 375 days. The films are observed after 152, 182, 211, 255 and 375days.

blooming after days* UV absorber of 152 182 211 255 375 Example 1 no nono no no Example 5 no no no no no *yes means a white deposit is clearlyobserved on the film surface indicating that migration or blooming hasoccurred. no means that no migration or blooming is observed.

EXAMPLE 205-(C₄₀-C₆₀Alkoxycarbonyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

Following the general procedure of Example5,5-carbomethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl-2H-benzotriazole(prepared as taught in British 2,319,035, Example 36) is substituted formethyl 3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydro-cinnamate.Using the polyethylene monoalcohol (average molecular weight 700), thetitle compound is obtained as a light yellow solid.

EXAMPLE 215-(C₂₀-C₄₀Alkoxycarbonyl)-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole

In a procedure similar to Example 20, the polyethylene monoalcohol(average molecular weight 700) is replaced with the polyethylenemonoalcohol (average molecular weight 460). The title compound isobtained as a light yellow solid.

EXAMPLES 22-33

Following the general procedure of Examples 20 and 21, the followingcompounds of formula I, where G₂ is G₃—X—CO—, G₃ is T₁ or T₂, and E₁ andE₂ are as indicated, are prepared.

Example* E₁ E₂ X G₃ T₁ 22 H tOc —O— T₁ C₂₀-C₄₀alkyl 23 H tOc —O— T₁C₃₀-C₅₀alkyl 24 H Do —NH— T₁ C₂₀-C₄₀alkyl 25 tBu Me —O— T₁ C₈₀-C₁₀₀alkyl26 tBu tBu —NH— T₁ C₂₀-C₄₀alkyl 27 tBu tBu —O— T₂ — 28 Ph Me —O— T₂ — 29Ph Do —NH— T₁ C₄₀-C₆₀alkyl 30 Al tOc —O— T₁ C₃₀-C₅₀alkyl 31 Cu Cu —O— T₁C₂₀-C₄₀alkyl 32 Cu Me —NH— T₁ C₃₀-C₅₀alkyl 33 Cu tOc —NH— T₁C₃₀-C₅₀alkyl *Al is allyl; tBu is tert-butyl; Cu is a-cumyl; Do isdodecyl; Me is methyl; tOc is tert-octyl; and Ph is phenyl.

EXAMPLE 345-[(3-C₃₇-C₅₇alkoxy-2-hydroxypropoxy)carbonyl]-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl-2H-benzotriazole

5-Carboxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl-2H-benzotriazole(prepared as taught in British 2,319,035, Example 37a) is reacted withthe glycidyl epoxide of the ethylene monoalcohol used in Example 5 inthe presence of toluene and tetrabutylonium bromide. The title compoundis prepared.

EXAMPLE 353-[3-(5-Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propylC₂₉-C₄₉Alkanoate

Using a procedure similar to that of Example 1,5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazoleand PERFORMACID® 550 (C₂₉-C₄₉alkanoic acid, New Phase Technologies,Piscataway, N.J.) are esterified. The title compound is obtained.

EXAMPLES 36-50

Following the general procedure of Example 35, the following compoundsof instant formula I are prepared where E₂ is the group—CH₂CH₂CH₂—X—CO—T₁; G₁ is H except for Example 39 where it is Cl; G₃ isabsent except for Examples 46 where it is methyl and Example 47 where itis octadecyl;

Example* E₁ G₂ X E₃ T₁ 36 H H —O— — C₁₉-C₃₉alkyl 37 tBu F —O— —C₁₉-C₃₉alkyl 38 tBu Cl —O— — C₂₉-C₄₉alkyl 39 Do Cl —O— — C₂₉-C₄₉alkyl 40Ph CN —O— — C₃₉-C₅₉alkyl 41 tBu H —O— — C₂₉-C₄₉alkyl 42 tBu —NO₂ —O— —C₁₉-C₃₉alkyl 43 tBu E₃SO₂ —O— nBu C₁₉-C₃₉alkyl 44 tBu E₃SO₂ —O— DoC₁₉-C₃₉alkyl 45 tBu E₃SO₂ —O— Ph C₁₉-C₃₉alkyl 46 Cu —COOG₃ —O— —C₂₉-C₄₉alkyl 47 Cu —COOG₃ —NH— — C₂₉-C₄₉alkyl 48 Cy PO(Ph)₂ —NH— —C₇₉-C₉₉alkyl 49 Cu CF₃ —O— — C₂₉-C₄₉alkyl 50 Cu CF₃ —NH— — C₃₉-C₅₉alkyl*nBu is n-butyl; tBu is tert-butyl; Cu is α-cumyl; Cy is cyclohexyl; Dois dodecyl; and Ph is phenyl.

EXAMPLES 51-65

Following the synthetic procedure outlined in Example 4, the followingcompounds of formula I are prepared where E₂ is —(CH₂)_(m)CO—X—T₄; G, isH except in Example 52 where it is Cl; E₃ is absent except in Example 57where it is ethyl, in Example 58 where it is dodecyl and in Example 59where it is phenyl; G₃ is absent except in Example 60 where it is butyland in Example 61 where it is octadecyl.

Example* E₁ G₂ X T₄ m T₁ 51 H H —O— T₁ 2 C₃₀-C₅₀alkyl 52 tBu Cl —O— T₂ 2— 53 tBu Cl —NH— T₁ 2 C₃₀-C₅₀alkyl 54 tBu Cl —O— T₂ 2 — 55 H F —NH— T₁ 2C₂₀-C₄₀alkyl 56 Do CN —O— T₁ 1 C₄₀-C₆₀alkyl 57 tBu E₃SO₂ —NH— T₁ 2C₃₀-C₅₀alkyl 58 Ph E₃SO₂ —O— T₂ 0 — 59 Cu E₃SO₂ —O— T₁ 2 C₃₀-C₅₀alkyl 60Cu —COOG₃ —O— T₁ 2 C₃₀-C₅₀alkyl 61 Cu —CONHG₃ —NH— T₁ 2 C₄₀-C₅₀alkyl 62H CF₃ —O— T₂ 2 — 63 tBu CF₃ —NH— T₁ 2 C₃₀-C₅₀alkyl 64 Cu CF₃ —O— T₁ 2C₂₀-C₄₀alkyl 65 Cu CF₃ —O— T₁ 1 C₈₀-C₁₀₀alkyl *tBu is tert-butyl; Cu isα-cumyl; Do is dodecyl; Ph is phenyl; and T₂ is a straight chain alkylof 30 to 50 carbon atoms.

EXAMPLE 663-[3-(5-Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-octyl-2-hydroxyphenyl]propylC₂₉-C₄₉Alkanoate

(A)5-Trifluoromethyl-2-(2-hydroxy-3-allyl-5-tert-octylphenyl)-2H-benzotriazole

This allyl intermediate is prepared as follows:

5-Trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole(13.01 g, 0.033 mol, the compound of Example 38 of British 2,319,035),potassium hydroxide (2.37 g, 0.036 mol) and ethanol (60 mL) are chargedto a reactor and stirred at ambient temperature for two hours. Allylbromide (4.84 g, 0.039 mol) and potassium iodide (0.34 g, 0.002 mol) areadded to the reaction mixture which is heated to 85° C. After holding at85° C. for 4.5 hours, the solvent is removed and replaced with 100 mL ofheptane. The mixture is washed thrice with 40 mL of water. The solventis then removed to yield 14.2 g of the corresponding O-allyl ether as anoff-white solid.

Analysis:

¹Hnmr (CDCl₃): δ 0.78 (s, 9H), 1.41 (s, 6H), 1.77 (s, 2H), 4.60-4.65 (d,2H), 5.16-5.34 (m. 2H), 5.86-6.00 (m, 1H), 7.06-7.11 (d, 1H), 7.49-7.54(dd, 1H), 7.61-7.67 (m, 2H), 8.08-8.12 (d, 1H), 8.35 (s, 1H)

The O-allyl compound (14.2 g) as prepared above is charged to a reactorand heated to 190-195° C. and held at that temperature for five hours.Flash column chromatography with silica gel and ethyl acetate/heptanesolvent as eluent to give the title compound in 12.2 g yield as a yellowoil.

Analysis:

Mass spectrometry: 432 (M+H);

¹Hnmr (CDCl₃): δ 0.78 (s, 9H), 1.46 (s, 6H), 1.81 (s, 2H), 3.53-3.64 (d,2H), 5.06-5.20 (m, 2H), 6.02-6.18 (m, 1H), 7.29-7.34 (d, 1H), 7.66-7.72(dd, 1H), 8.05-8.12 (d, 1H), 8.29-8.35 (m, 2H), 11.17 (s, 1H)

(B) Preparation of the Corresponding 3-hydroxypropyl Intermediate.

The allyl intermediate formed in section (A) above is subjected tohydroboration conditions described by Brown in “Boranes in OrganicChemistry”, Cornell University Press, Ithaca, N.Y. 1972, and by J. Marchin “advanced Organic Chemistry”, 2nd Edition, McGraw-Hill, New York,1977, page 718.

(C) Preparation of the Title Compound

Using synthetic conditions analogous to those of Example 1,5-trifluoromethyl-2-[2-hydroxy-3-(3-hydroxypropyl)-5-tert-octylphenyl]-2H-benzotriazoleand C_(29-C) ₄₉alkanoic acid (PERFORMACID® 550, New Phase Technologies,Piscataway, N.J.) are reacted to form the title compound ester.

EXAMPLES 67-81

Using the synthetic procedure similar to that of Example 66, the instantcompounds of formula I where E₁ is —CH₂CH₂CH₂—X—CO—T₁ are prepared whereG₁ is hydrogen except in Example 70 where it is Cl;

Example* E₂ G₂ X E₃ G₃ T₁ 67 Me H —O— — — C₁₉-C₃₉alkyl 68 tBu H —NH— — —C₂₉-C₄₉alkyl 69 tBu Cl —O— — — C₁₉-C₃₉alkyl 70 tBu Cl —NH— — —C₂₉-C₄₉alkyl 71 tOc F —O— — — C₂₉-C₄₉alkyl 72 tOc CN —O— — —C₆₉-C₈₉alkyl 73 tOc E₃SO₂ —O— Ocd — C₁₉-C₃₉alkyl 74 tOc E₃SO₂ —O— Ph —C₂₉-C₄₉alkyl 75 Do E₃SO₂ —NH— nBu — C₂₉-C₄₉alkyl 76 Cu —COOG₃ —NH— — MeC₂₉-C₄₉alkyl 77 Cu —COOG₃ —O— — ** C₂₉-C₄₉alkyl 78 Cu —COOG₃ —O— — ***C₂₉-C₄₉alkyl 79 Cu CF₃ —NH— — — C₂₉-C₄₉alkyl 80 tOc CF₃ —O— — —C₂₉-C₄₉alkyl 81 Me CF₃ —O— — — C₇₉-C₉₉alkyl *nBu is n-butyl; tBu istert-butyl; Cu is α-cumyl; Do is dodecyl; Me is methyl; Ocd isoctadecyl; tOc is tert-octyl; and Ph is phenyl. **is C₃₀-C₅₀alkyl. ***isC₂₀-C₄₀alkyl.

EXAMPLE 82Methylene-[2-(4-tert-octyl-6-(5-trifluoromethyl)-2H-benzotriazol-2-yl)phenol]{2′-[4-(C₃₀-C₅₀alkoxycarbonylethyl)-6-(5-trifluoromethyl)-2H-benzotriazol-2-yl}phenol}

Following the general procedure disclosed in EP 924,203 A1, the titlecompound is prepared.

EXAMPLES 83-100

Using the synthetic procedure similar to that of Example 82, the instantcompounds of formula III where in Examples 83-84 and 95, G₃ isC₃₀-C₅₀alkyl; and where in Examples 88-90, E₃ is respectively phenyl,butyl and dodecyl.

Example* G₂ G₂′ E₂ E₂′ L T₁ 83 COOG₃ H CH₃ CH₃ M — 84 COOG₃ COOG₃ tOcCH₃ M — 85 Cl Cl EtCONHT₁ Do M C₂₀-C₄₀alkyl 86 Cl Cl EtCOOT₁ (E₂) MC₃₀-C₅₀alkyl 87 F F EtCOOT₁ (E₂) mX C₃₀-C₅₀alkyl 88 E₃SO₂ (G₂) EtCOOT₁CH₃ mX C₂₀-C₄₀alkyl 89 E₃SO₂ Cl tOc EtCOOT₁ M C₃₀-C₅₀alkyl 90 E₃SO₂ HtOc PrOCOT₁ M C₂₉-C₄₉alkyl 91 CN CN tBu PrOCOT₁ M C₁₉-C₃₉alkyl 92 CF₃CF₃ PrOCOT₁ (E₂) M C₂₉-C₄₉alkyl 93 CF₃ H EtCOOT₁ (E₂) M C₃₀-C₅₀alkyl 94CF₃ H PrOCOT₁ (E₂) mX C₂₉-C₄₉alkyl 95 COOG₃ CF₃ CH₃ tOc M — 96 Ph₂PO(G₂) EtCOOT₁ (E₂) M C₃₀-C₅₀alkyl 97 Ph₂PO (G₂) EtCOOT₁ (E₂) mXC₂₀-C₄₀alkyl 98 Cl H EtCONHT₁ (E₂) M C₃₀-C₅₀alkyl 99 F F EtCONHT₁ (E₂) MC₂₀-C₄₀alkyl 100  CF₃ CF₃ EtCONHT₁ (E₂) M C₃₀-C₅₀alkyl *tBu istert-butyl; Do is dodecyl; M is methylene; tOc is tert-octyl; mX ism-xylylene; in EtCONHT₁, Et is ethylene; in PrOCOT₁, Pr is trimethylene.When under G₂′ the term (G₂) appears, G₂′ has the same meaning as G₂;and when under E₂′ the term (E₂) appears, E₂′ has the same meaning asE₂.

EXAMPLE 1015-[ωButyloxy-poly(propyleneoxy)]carbonyl2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,

5-Carboxymethoxy-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole,propylene glycol) monobutyl ether (average molecular weight 1000) anddibutyltin oxide ated to 170° C. under vacuum for four hours. The titlecompound is obtained as a light yellow viscous oil.

EXAMPLE 102 ωButyloxy-1-[poly(1,2-butyleneoxy)-2-ethyl]ethyl3-(5-Trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

Following the procedure of Example 3, an equivalent amount ofpoly(1,2-butylene glycol) monobutyl ether, with an average molecularweight of 1500, is substituted for the polyethylene monoalcohol to givethe title compound as a light yellow viscous oil.

EXAMPLE 103 ωHydroxy-poly(butyleneoxy)butyl3-(5-Chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate

Following the procedure of Example 2, an equivalent amount ofpolytetrahydrofuran, linear polymer of average molecular weight of 1400,TERATHANE®, is substituted for the polyethylene monoalcohol to give thetitle compound as a light yellow viscous oil.

EXAMPLE 104 Color Change of a White Un scented Candle Wax underFluorescent Lamp Exposure

A variety of different stabilizers are evaluated in a white unscentedcandle wax under fluorescent lamp exposure. The stabilizers include acompound of Example 2 alone or with a hindered aminebis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA orbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN®123, CIBA. The ΔE values represent the change in color after exposure. Alow ΔE value indicates less change in color and is highly desired.

The instant compound alone or with the hindered amine provides excellentprotection to the white unscented candle wax from discoloration.

EXAMPLE 105 Color Fade of Green Scented Candle Wax under UV LampExposure

A variety of different stabilizers are evaluated in green scented candlewax obtained from the Candle Corporation of America under UV lampexposure at 368 nm wavelength. The stabilizers include a compound ofExample 1 alone or with a hindered aminebis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA orbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN®123, CIBA. The ΔE values represent the change in color after exposure. Alow ΔE value indicates less change in color and is highly desired.

The instant compound alone or with the hindered amine provides excellentprotection to the green scented candle wax from dye fade.

EXAMPLE 106 Color Fade of a Blue Unscented Candle Wax under UV LampExposure

A variety of different stabilizers are evaluated in blue unscentedcandle wax under UV lamp exposure at 368 nm wavelength. The stabilizersinclude a compound of Example 3 alone or with a hindered aminebis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN® 292, CIBA orbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN®123, CIBA. The ΔE values represent the change in color after exposure. Alow ΔE value indicates less change in color and is highly desired.

The instant compound alone or with the hindered amine provides excellentprotection to the blue unscented candle wax from dye fade.

EXAMPLE 107

To a poly(ethylene terephthalate), PET, resin is added 0.5% by weight ofa compound of Example 1 based on the resin. The stabilized resin is thenblow or injection molded into a PET bottle from which the UV absorbercompound of Example 1 resists blooming or migration from the resin.

EXAMPLE 108 Color Fade of Pink Scented Candle Wax under Fluorescent LampExposure

Different stabilizers are evaluated in pink scented candle wax obtainedfrom the Candle-Lite Corporation under fluorescent lamp exposure. The ΔEvalues represent the change in color after the indicated days ofexposure. A low ΔE value indicates less change in color and is highlydesired.

ΔE after Sample* (wt % add) 25 days Blank (no add) 12.47 A (0.3%) 8.91 D(0.3%) 9.38 B (0.15%) + 6.20 C (0.15%) A (0.15%) + 3.23 D (0.15%) E(0.15%) + 2.46 D (0.15%) *A is octyl3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN ®384, CIBA. B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,TINUVIN ® 329, CIBA. C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ®81, CIBA. D is bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate,TINUVIN ® 292, CIBA. E is C₂₀-C₄₀alkyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate,compound of Example 3.

These data show that a hindered amine in combination with an instant UVabsorber protects the pink scented candle wax far better than thehindered amine or a UV absorber alone.

EXAMPLE 109 Color Fade of Pink Scented Candle Wax under UV Lamp Exposure

A variety of different stabilizers are evaluated in pink scented candlewax obtained from the Candle-Lite Corporation under UV lamp exposure.The ΔE values represent the change in color after the indicated days ofexposure. A low ΔE value indicates less change in color and is highlydesired.

ΔE after Sample* (wt % add) 32 days Blank (no add) 21.10 D (0.3%) 16.24B (0.15%) + C (0.15%) 11.15 A (0.15%) + D (0.15%)  9.84 E (0.15%) + D(0.15%)  5.19 F (0.15%) + G (0.15%)  5.63 *A is octyl3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN ®384, CIBA. B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,TINUVIN ® 329, CIBA. C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ®81, CIBA. D is bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,TINUVIN ® 292, CIBA. E is C₂₀-C₄₀alkyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate,compound of Example 3. F isbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN ®123, CIBA). G is C₂₀-C₄₀alkyl3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, compoundof Example 1.

These data show that a hindered amine in combination with an instant UVabsorber protects the pink scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 110 Color Fade of Gray Scented Candle Wax under Fluorescent LampExposure

A variety of different stabilizers are evaluated in gray scented candlewax obtained from the Candle-Lite Corporation under fluorescent lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired.

ΔE after Sample* (wt % add) 29 days Blank (no add) 15.72  A (0.3%) 9.88F (0.3%) 11.57  D (0.3%) 7.63 B (0.15%) + C (0.15%) 8.01 A (0.15%) + F(0.15%) 3.20 E (0.15%) + D (0.15%) 2.56 *A is octyl3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN ®384, CIBA. B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,TINUVIN ® 329, CIBA. C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ®81, CIBA. D is bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,TINUVIN ® 292, CIBA. E is C₂₀-C₄₀alkyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate,compound of Example 3. F isbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN ®123, CIBA).

These data show that a hindered amine in combination with an instant UVabsorber protects the gray scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 111 Color Fade of Gray Scented Candle Wax under UV Lamp Exposure

A variety of different stabilizers are evaluated in gray scented candlewax obtained from the Candle-Lite Corporation under UV lamp exposure.The ΔE values represent the change in color after the indicated days ofexposure. A low ΔE value indicates less change in color and is highlydesired.

ΔE after Sample* (wt % add) 18 days Blank (no add) 29.97  A (0.3%) 8.82F (0.3%) 26.96  B (0.15%) + C (0.15%) 10.21  A (0.15%) + F (0.15%) 5.04G (0.15%) + F (0.15%) 4.86 H (0.15%) + I (0.15%) 3.54 E (0.15%) + D(0.15%) 3.28 *A is octyl3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, TINUVIN ®384, CIBA. B is 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole,TINUVIN ® 329, CIBA. C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ®81, CIBA. D is bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,TINUVIN ® 292, CIBA. E is C₂₀-C₄₀alkyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamate,compound of Example 3. F isbis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, TINUVIN ®123, CIBA). G is C₂₀-C₄₀alkyl3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, compoundof Example 1. H is C₂₀-C₄₀alkyl3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,compound of Example 2. I is1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-4-octadecanoyloxypiperidine.

These data show that a hindered amine in combination with an instant UVabsorber protects the gray scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 112 Color Fade of White Scented Candle Wax under FluorescentLamp Exposure

A variety of different stabilizers are evaluated in white scented candlewax obtained from the Candle-Lite Corporation under fluorescent lampexposure. The ΔE values represent the change in color after theindicated days of exposure. A low ΔE value indicates less change incolor and is highly desired.

ΔE after Sample* (wt % add) 24 days Blank (no add) 34.34 A (0.3%) 29.16D (0.3%) 32.33 F (0.3%) 24.30 B (0.15%) + C (0.15%) 20.08 A (0.15%) + D(0.15%) 31.06 G (0.15%) + F (0.15%)  7.98 H (0.15%) + J (0.15%)  7.55 *Ais octyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,TINUVIN ® 384, CIBA. B is2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, TINUVIN ® 329, CIBA.C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ® 81, CIBA. D isbis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN ® 292, CIBA.F is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,TINUVIN ® 123, CIBA). G is C₂₀-C₄₀alkyl3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, compoundof Example 1. H is C₂₀-C₄₀alkyl3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,compound of Example 2. J is2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)amino-s-triazine.

These data show that a hindered amine in combination with an instant UVabsorber protects the white scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

EXAMPLE 113 Color Fade of White Scented Candle Wax under UV LampExposure

A variety of different stabilizers are evaluated in white scented candlewax obtained from the Candle-Lite Corporation under UV lamp exposure.The ΔE values represent the change in color after the indicated days ofexposure. A low ΔE value indicates less change in color and is highlydesired.

ΔE after Sample* (wt % add) 25 days Blank (no add) 45.09 A (0.3%) 25.50F (0.3%) 36.32 D (0.3%) 32.03 B (0.15%) + C (0.15%) 30.11 A (0.15%) + D(0.15%) 29.74 F (0.15%) + G (0.15%) 13.53 H (0.15%) + J (0.15%)  9.03 *Ais octyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,TINUVIN ® 384, CIBA. B is2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, TINUVIN ® 329, CIBA.C is 4-octyloxy-2-hydroxybenzophenone, CHIMASSORB ® 81, CIBA. D isbis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, TINUVIN ® 292, CIBA.F is bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,TINUVIN ® 123, CIBA). G is C₂₀-C₄₀alkyl3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, compoundof Example 1. H is C₂₀-C₄₀alkyl3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,compound of Example 2. J is2-(2-hydroxyethylamino)-4,6-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)amino-s-triazine.

These data show that a hindered amine in combination with an instant UVabsorber protects the white scented candle wax far better thanconventional UV absorbers or a hindered amine alone.

What is claimed is:
 1. A composition which comprises (a) candle waxwhich is white and unscented; white and scented; dyed and unscented;dyed and scented; dipped and unscented; or dipped and scented, and (b)an effective stabilizing amount of a (i) a compound of formula I, II orIII

wherein G₁ and G₁′ are independently hydrogen or halogen, G₂ and G₂′ areindependently hydrogen, halogen, nitro, cyano, E₃SO—, E₃SO₂—, —COOG₃,perfluoroalkyl of 1 to 12 carbon atoms, —P(O)(C₆H₅)₂, —CO—G₃, —CO—NH—G₃,—CO—N(G₃)₂, —N(G₃)—CO—G₃,

G₃ is hydrogen, straight or branched chain alkyl of 1 to 24 carbonatoms, straight of branched chain alkenyl of 2 to 18 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms,phenyl, or said phenyl or said phenylalkyl substituted on the phenylring by 1 to 4 alkyl of 1 to 4 carbon atoms; or G₃ is T₁ or T₂, E₁ ishydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms,straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkylof 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, orsaid phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4alkyl of 1 to 4 carbon atoms; or E₁ is alkyl of 1 to 24 carbon atomssubstituted by one or two hydroxy groups; or E₁ is the group—(CH₂)_(m)—CO—X—T₁ where m is 0, 1 or 2; or E₁ is the group—(CH₂)_(p)—X—CO—T₂ where p is 1, 2 or 3; E₂ and E₂′ are independentlystraight or branched alkyl chain of 1 to 24 carbon atoms, straight orbranched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or saidphenyl or said phenylalkyl substituted on the phenyl ring by one tothree alkyl of 1 to 4 carbon atoms; or E₂ and E₂′ are independently saidalkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atomssubstituted by one or more —OH, —OCOE₁₁, —OE₄, —NH₂, —NHCOE₁₁, —NHE₄ or—N(E₄)₂, or mixtures thereof, where E₄ is straight or branched chainalkyl of 1 to 24 carbon atoms; or said alkyl or said alkenyl interruptedby one or more —O—, —NH—or —NE₄—groups or mixtures thereof and which canbe unsubstituted or substituted by one or more —OH, —OE₄ or —NH₂ groupsor mixtures thereof; or E₂ and E₂′ are independently —(CH₂)_(m)—CO—X—T₁or —(CH₂)_(p)—X—CO—T₂, or E₄ is T₁ or T₂, X is —O— or —N(E₁₆)—, E₁₆ ishydrogen, C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms,or is cyclohexyl or C₇-C₁₅ aralkyl, E₁₁ is a straight or branched chainC₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, straight or branched chain C₂-C₁₈alkenyl,C₆-C₁₄aryl or C₇-C₁₅aralkyl; or E₁₁ is T₁ or T₂, E₃ is alkyl of 1 to 20carbon atoms, hydroxyalkyl of 2 to 20 carbon atoms, alkenyl of 3 to 18carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted byone or two alkyl of 1 to 4 carbon atoms or1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6to 16 carbon atoms, L is alkylene of 1 to 12 carbon atoms, alkylidene of2 to 12 carbon atoms, benzylidene, p-xylylene, α,α,α′,α′-tetramethyl-m-xylene or cycloalkylidene, and T is —SO—, —SO₂—,—SO—E—SO—, —SO₂—E—SO₂—, —CO—, —CO—CH₂—CO—, —CO—E—CO—, —COO—E—OCO—or—CO—NG₅—E—NG₅—CO—, where E is alkylene of 2 to 12 carbon atoms,cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted orterminated by cyclohexylene of 8 to 12 carbon atoms; G₅ is G₃ orhydrogen, T₁ is straight or branched chain alkyl of 25 to 100 carbonatoms, or said alkyl substituted by one hydroxyl group and interruptedby one oxa moiety, or a mixture of such alkyl moieties; or T₁ is—(R—O)_(n—R—OG) _(x) where R is ethylene, propylene, trimethylene,1,2-butylene or tetramethylene, and n is 6 to 49 so that the totalnumber of carbon atoms in T₁ is at least 25, G_(x) is hydrogen, straightor branched chain alkyl of 1 to 24 carbon atoms, straight of branchedchain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbonatoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl orsaid phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to4 carbon atoms, T₂ is straight or branched alkyl of 23 to 100 carbonatoms; and with the proviso that at least one of E₁, E₂ and E₂′ is agroup —(CH₂)_(m)—CO—X—T₁ or a group —(CH₂)_(p)—X—CO—T₂ or at least oneof G₂ and G₂′ is a group —COOG₃, —CO—G₃, —CO—NH—G₃, —CO—N(G₃)₂,—N(G₃)—CO—G₃,

where G₃ is T₁ or T₂.
 2. A composition according to claim 1 wherein theeffective amount of benzotriazole in the candle wax is 0.01 to 10% byweight based on the wax.
 3. A composition according to claim 1 whereinthe benzotriazole is (a) C₂₀-C₄₀alkyl3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, (b)C₂₀-C₄₀alkyl3-(5-chloro-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,(c) C₂₀-C₄₀alkyl3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,(d) C₂₀-C₄₀alkyl3-(5-phenylsulfonyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate,or (e) C₄₀-C₆₀alkyl3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate.
 4. Acomposition according to claim 1 which additionally comprises a phenolicantioxidant, phosphite, long chain N,N-dialkylhydroxylamine, nitrone oramine oxide.
 5. A composition according to claim 4 which additionallycomprises a phenolic antioxidant which is selected from the groupconsisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate),di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,3,6-dioxaoctamethylenebis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate),2,6di-tert-butyl-p-cresol, 2,2′-ethylidene-bis(4,6-di-tert-butylphenol),1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocynurate,1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane,1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl) mesitol,hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate),1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide),calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate),ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, andN,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]oxamide.6. A composition according to claim 1 which additionally comprises aneffective amount of a (ii) hindered amine, wherein the ratio by weightof (i) to (ii) is from 10:1 to 1:10.
 7. A composition according to claim6 wherein the effective amount of benzotriazole plus the hindered aminein the candle wax is 0.01 to 10% by weight based on the wax.
 8. Acomposition according to claim 6 wherein the hindered amine isbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate,di(1,2,2,6,6-pentamethylpiperidin-4-yl)(3,5-di-tert-butyl-4-hydroxybenzyl)-butylmalonate, the polycondensationproduct of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidineand succinic acid, the polycondensation product of2,4-dichloro-6-tert-octylamino-s-triazine and4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),N,N′,N″,N″′-tetrakis[(4,6-bis(butyl-(1,2,2,6,6-pentamethylpiperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane,di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine,poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino],2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine,1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,or2-(2-hydroxyethylamino)-4,6-bis[N-butyl—N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-s-triazine.